CN1185687C - Detergent for lithography - Google Patents

Detergent for lithography Download PDF

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Publication number
CN1185687C
CN1185687C CNB988008149A CN98800814A CN1185687C CN 1185687 C CN1185687 C CN 1185687C CN B988008149 A CNB988008149 A CN B988008149A CN 98800814 A CN98800814 A CN 98800814A CN 1185687 C CN1185687 C CN 1185687C
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CN
China
Prior art keywords
resist
ethanol
cleaning agent
weight ratio
propylene glycol
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Expired - Fee Related
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CNB988008149A
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Chinese (zh)
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CN1229522A (en
Inventor
武田贵志
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Clariant International Ltd
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Clariant Finance BVI Ltd
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Publication of CN1229522A publication Critical patent/CN1229522A/en
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/42—Stripping or agents therefor
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3227—Ethers thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/261—Alcohols; Phenols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/263—Ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/264—Aldehydes; Ketones; Acetals or ketals
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/266—Esters or carbonates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/50—Solvents
    • C11D7/5004—Organic solvents
    • C11D7/5022—Organic solvents containing oxygen
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/16—Coating processes; Apparatus therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/42—Stripping or agents therefor
    • G03F7/422—Stripping or agents therefor using liquids only
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3105—After-treatment
    • H01L21/311—Etching the insulating layers by chemical or physical means
    • H01L21/31127—Etching organic layers
    • H01L21/31133—Etching organic layers by chemical means
    • C11D2111/20—

Abstract

The present invention relates to a cleaner for lithography which is excellent in the ability to dissolve a resist and highly safe to the human body and which can be used usefully to clean a coater such as in a coater cup, to remove an unnecessary resist from a substrate when or after coating of a resist, to remove the resist from the substrate after the object using the resist was achieved, and to clean and rinse the substrate after removal of the resist. The cleaner for lithography comprises a homogeneous solution of at least one organic solvent selected from the group consisting of propylene glycol alkyl ether, propylene glycol alkyl ether acetate, ethylene glycol alkyl ether, ethylene glycol alkyl ether acetate, acetic acid alkyl ester, propionic acid alkyl ester, alkoxypropionic acid alkyl ester, lactic acid alkyl ester, aliphatic ketone, and alkoxybutanol and at least one selected from alcohols having alkyl group with 1 to 4 carbon atoms.

Description

Detergent for lithography
Invention field
The present invention relates to a kind of lithographic cleaning agent that is used for, this cleaning agent has excellent dissolving or removes the ability of resist and as safe as a house to human body, this cleaning agent can be used for cleaning various applicators usually, as coating cup, when the coating resist or behind the coating resist, remove unnecessary resist from matrix, after using resist to reach target, remove resist, cleaning and rinsing matrix after removing resist from matrix.
Background of invention
For producing integrated circuit component, colour filter, liquid crystal display cells etc., adopting the lithographic printing of resist is conventional method.For example, when adopting lithography to produce integrated circuit component etc., on matrix, form one deck antireflecting coating in case of necessity earlier, and then form positivity or negative resist thereon, except that desolvating, on resist layer, form one deck antireflecting coating by baking in case of necessity again, carry out irradiations such as ultraviolet ray, far ultraviolet, electron beam X ray then, toast again in case of necessity, obtain a kind of resist figure.After this, toast in case of necessity, matrix is carried out etching etc., remove resist again.
For resist coating, can adopt the whole bag of tricks, be coated with method, knife coating, dip coating etc. as spin-coating method, rolling method, contrary rolling method, curtain coating.For example, when producing integrated circuit component, the main method of coating resist is to adopt spin-coating method.In spin-coating method, on matrix, by the matrix rotation, the resist solution of described drippage can extend towards the matrix periphery with the resist drips of solution, thereby excessive resist solution is removed from the scattering of matrix periphery, thereby formed resist layer with required film thickness degree.The excessive resist of part still is retained in the paint cup, can solidify when solvent evaporation.Material after the curing can become fine powder, and this fine powder meeting scattering also adheres on the matrix, thereby causes the resist graphic defects.In order to prevent that this phenomenon from taking place, must be every several to paint cup of several matrix cleanings.And then, when the resist layer with desired thickness by spin-coating method after forming on the matrix, the shortcoming that exists is, part resist solution can further move to the back side of matrix, perhaps resist solution still thicker on the periphery of matrix (promptly forming bead), thereby, just must remove resist or bead on unnecessary resist or matrix side, periphery or the back side.In addition, even in other coating method, also can be as in spin-coating method, resist and unsuitable part adhere to.Carry out to remove resist usually after etching etc. handles in matrix,, also adopt organic solvent dissolution usually and remove resist even remove in the step at this.
Normally adopt purified water etc. to clean by course of dissolution from the surface of the matrix of wherein removing resist and make it free of contamination, thereby can remove the fine particle that exists on the stromal surface, after this, carry out subsequent operation again.If being used to remove the solution of resist is water-insoluble organic solvents or amine type organic solvent, then after removing the resist step, matrix usually must be carried out rinsing again with a kind of water-miscible organic solvent of cleaning, rather than cleans with purified water immediately.Its reason is, if adopt water-insoluble organic solvents as the organic solvent of removing resist, then by preventing that it is deposited in the solvent when mixing with purified water, thereby the resist that prevents to be dissolved in this solvent adheres to matrix again, its reason is that also the water-insoluble organic solvents that is present on the stromal surface can be replaced by water-miscible organic solvent so that the replacement of purified water.If use amine type organic solvent as the liquid that is used to remove resist, then this solvent can be retained in the purified water, makes water be alkalescence, thereby can stop metal matrix to corrode.
After finishing applying step, should clean applicator so that reuse or as being used for the applicator of other material, perhaps, if when between matrix and resist layer, having antireflecting coating, then after forming the resist figure, useable solvents is removed antireflecting coating in case of necessity.
As previously mentioned, in the various steps of lithographic process, all use cleaning agent, and as this class cleaning agent, at present known by the various cleaning agents of forming by organic solvent (for example, Japanese Patent Application Publication is 4-49938 number).
But, some conventional cleaning agent that adopts needs expensive time or consumption very big, this be because, the ability of their dissolving resists is relatively poor, and some is also poisonous, thereby, also there is not at present a kind of cleaning agent can satisfy the excellent solvent performance simultaneously and to the requirement of this two aspect of human body safety, therefore, promptly have solvent nature and again the solvent of human body safety is still that people wish to obtain.Though the production process of integrated circuit component has been described above,, the application not only is used to produce integrated circuit component, and can be used for producing colour filter, liquid crystal display cells etc.
The purpose of this invention is to provide a kind of lithographic cleaning agent that is used for, there are not the problems referred to above in it, that is to say, the invention provides a kind of cleaning agent, this cleaning agent can be used for cleaning various applicators usually, as coating cup, removes unnecessary resist from matrix when the coating resist or behind the coating resist, after using resist to reach target, remove resist, cleaning and rinsing matrix after removing resist from matrix; This cleaning agent has very high solubility property, can effectively clean rapidly with a small amount of cleaning agent, and this cleaning agent is as safe as a house to human body.
Invention is described
Through further investigation, the present inventor finds, uses the homogeneous mixture of specific organic solvent and certain alcohols can achieve the above object as being used for lithographic cleaning agent, thereby has finished the present invention.
The invention provides a kind of lithographic cleaning agent that is used for, described cleaning agent is made up of a kind of homogeneous solution, and described homogeneous solution has the composition of one of the following,
Propylene glycol monomethyl ether and ethanol, weight ratio are 9: 1～1: 1,
Propylene glycol monomethyl ether and 1-propyl alcohol, weight ratio are 9: 1～3: 2,
Propylene glycol monomethyl ether and 2-propyl alcohol, weight ratio are 9: 1～3: 2,
Propylene glycol monomethyl ether, ethanol and 1-propyl alcohol, weight ratio is 7: 2: 1,
Propylene glycol monomethyl ether and ethanol, weight ratio are 9: 1～3: 2,
N-butyl acetate and ethanol, weight ratio are 7: 3,
Ethyl lactate and ethanol, weight ratio are 7: 3,
2-heptanone and ethanol, weight ratio are 7: 3,
Ethoxyl ethyl propionate and ethanol, weight ratio are 7: 3,
Ethylene glycol monoethyl ether acetate and ethanol, weight ratio are 7: 3, or
Methoxybutanol and ethanol, weight ratio are 7: 3.
Among the present invention, preferred solvent is a following solvents:
(1) propylene glycol C 1-4Alkyl ether is as propylene glycol monomethyl ether, propylene glycol list ethylether, propylene glycol list propyl ether, propylene glycol list n-butyl ether etc.;
(2) propylene glycol C 1-4The alkyl ether acetic acid esters is as propylene glycol monomethyl ether, propylene glycol list ethylether acetic acid esters etc.;
(3) ethylene glycol C 1-4Alkyl ether is as glycol monomethyl methyl ether, ethylene glycol monomethyl ether, glycol monomethyl propyl ether etc.;
(4) ethylene glycol C 1-4The alkyl ether acetic acid esters is as ethylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate etc.;
(5) acetate C 1-4Arrcostab is as propyl acetate, n-butyl acetate etc.;
(6) propionic acid C 1-4Arrcostab is as methyl propionate, ethyl propionate, propyl propionate, butyl propionate etc.;
(7) C 1-4Alkoxyl propionic acid C 1-4Arrcostab is as methoxypropionic acid methyl esters, ethoxyl ethyl propionate, methoxy propyl acetoacetic ester, ethoxy-propionic acid methyl esters etc.;
(8) lactic acid C 1-4Arrcostab is as methyl lactate, ethyl lactate etc.;
(9) C 2-8Aliphatic ketone is as 2-butanone, 2 pentanone, methyl-n-butyl ketone, 2-heptanone etc.;
(10) C 1-4The alkoxyl butanols is as methoxybutanol, ethyoxyl butanols etc.
Particularly preferably be in the solvent of more than enumerating: propylene glycol monomethyl ether, propylene glycol list ethylether, propylene glycol list propyl ether, propylene glycol monomethyl ether, propylene glycol list ethylether acetic acid esters, ethylene glycol monomethyl ether acetate, n-butyl acetate, methoxypropionic acid methyl esters, ethoxyl ethyl propionate, ethyl lactate, 2-heptanone and methoxybutanol.
Organic solvent can be used singly or in combination.Preferred two or more organic solutions are used in combination, and comprise the combination of propylene glycol alkyl ether and propylene glycol alkyl ether acetic acid ester, the combination of preferred especially propylene glycol monomethyl ether and propylene glycol monomethyl ether.
Comprise methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, 1-butanols etc. though have the alcohol of the alkyl of 1～4 carbon atom, consider fail safe, preferred acetate, 1-propyl alcohol and 2-propyl alcohol.These alcohol can be used alone or in combination.The combination of two or more alcohol for example comprises: the combination of the combination of ethanol and 1-propyl alcohol and ethanol and 2-propyl alcohol.
Though the preferred embodiment of organic solvent or alcohol as mentioned above, can be used for organic solvent among the present invention or alcohol and be not limited to these certainly and specify.
Organic solvent can change according to organic solvent that is adopted or employed compound mode with the mixing ratio of alcohol.But organic solvent is generally 10: 90 with the mixed weight ratio of alcohol～and 99: 1, preferred 40: 60～90: 10, first-selected 60: 40～80: 20 (below, " ratio " all refers to weight).
The present invention is used for the lithographic printing that lithographic cleaning agent can be used for any positivity of employing well known in the art or negative resist.The representative instance that is used for the resist that lithographic cleaning agent can use of the present invention comprises: positive corrosion-resisting agent, for example resist of being made up of quinone diazide sensitising agent and alkali soluble resins and chemical reinforced slushing compound; Negative resist, for example comprise the polymer with photosensitive group such as cinnamic acid polyvinylesters resist, comprise the aromatics azide resist, comprise the azide of forming by thermoprene and diazide resist, comprise the resist of azo resin, but comprise the photopolymerizable composition of the unsaturated compound of addition polymerization, the negative resist of chemical modification etc.
The above-mentioned resist material of being made up of quinone diazide sensitising agent and alkali soluble resins is the material that preferably applies cleaning agent of the present invention, being used for the quinone diazide sensitising agent of resist material and the example of alkali soluble resins comprises: quinone diazide sensitising agent, as 1,2-benzoquinones diazido-4-sulfonic acid, 1,2-naphthoquinones diazido-4-sulfonic acid, 1,2-naphthoquinones diazido-5-sulfonic acid, the ester of these sulfonic acid or acid amides; The copolymer of alkali soluble resins such as polyvinyl phenol, polyvinyl alcohol, acrylic or methacrylic acid and novolac resin, described novolac resin is made with aldehyde such as formaldehyde, paraformaldehyde etc. by one or more phenol such as phenol, o-cresol, m-cresol, p-cresol, xylenols etc.
Chemical reinforced slushing compound also is a kind of resist that preferably applies cleaning agent of the present invention on it.The resist that chemistry strengthens produces a kind of acid behind radiating irradiation, because the chemical change that the catalytic action of this acid takes place, the dissolubility of the illuminated portion in developing solution changes and forms a kind of figure, for example, the resist that can mention is made up of the acid-producing cpd that forms a kind of acid behind radiating irradiation and a kind of resin that contains the acid-sensitive group, described resin can decompose in the presence of acid, form a kind of alkali solubility group such as phenol hydroxyl or carboxyl, also the resist that can mention is made up of alkali soluble resins, crosslinking agent and acid-producing agent.
The present invention is used for lithographic cleaning agent can be coated with that to add to some its solvent be the composition of organic solvent, described composition comes from the known compositions that is used to apply antireflecting coating, it is used to prevent the reverberation when matrix is avoided shining, or is used for preventing that at resist layer light taking place disturbs.
The coating of cleaning agent of the present invention is specific as follows with the method that forms the resist figure: at first, adopt known coating method such as spin-coating method that resist solution is coated on above silicon matrix, the glass matrix etc., answer preheating in case of necessity.In case of necessity, coating and formation one deck anti-reflecting layer before or after resist coating.If this coating is formed by for example spin-coating method; then the resist bead of antireflecting coating can form in the edge of matrix; but the flowability of bead can by spray cleaning agent of the present invention to be positioned at the rotation edge bead on, thereby can on matrix, form resist layer or antireflecting coating with basic uniform thickness.In addition, the antireflection that moves to the periphery or the matrix back side is wanted and can be removed by spraying cleaning agent to this part.
The resist that applies on the matrix as carry out prebake conditions on heating plate, is removed and desolvates, thereby form resist layer, its thickness is generally about 1～2.5 μ m.Prebake conditions is normally at 20～200 ℃, carries out under preferred 50～150 ℃, and certainly, temperature can be according to the type change of solvent that is adopted or resist.Thereby, resist layer can carry out irradiation by known irradiation devices by screen in case of necessity, as high-pressure mercury lamp, metal halide lamp, ultrahigh pressure mercury lamp, KrF excimer laser, ArF excimer laser, gentle x-ray irradiation device, electron beam stretching device etc., after irradiation, carry out the back baking in case of necessity, to improve developing performance, resolution, graphics shape etc., subsequently, develop, obtain the resist figure.The development of resist is normally by adopting the alkali developing solution to carry out.The alkali developing solution that is adopted is aqueous solution, Tetramethylammonium hydroxide (TMAH) of water or NaOH etc.
After forming the resist figure, the processing that the resist figure can be used for being scheduled to as etching, spraying plating, ions diffusion (ion diffusion) etc., to form circuit element, adopts cleaning agent of the present invention can remove the resist figure.After removing, available in case of necessity cleaning agent of the present invention carries out rinsing.And then when the solvent that is used to remove resist during for water-insoluble solvent different with the present invention or amine type organic solvent, cleaning agent of the present invention is used to rinsing where necessary, carries out rinsing with pure water again.In addition, cleaning agent of the present invention can be used to clean coating effectively.
Optimum implementation
Below, further describe the present invention by embodiment and reference example, still, they are not construed as limiting the invention.
Embodiment 1
The quinone diazido sensitising agent of the following novolac resin of 100 weight portions and 24 weight portions is dissolved in the third diether monomethyl ether acetate of solids content 25wt% and makes resist.This resist is spin-coated on the silicon matrix after 4 inches the prebake conditions, making coating layer thickness is 2 μ m, then, with its on the directly-heated type heating plate in 100 ℃ of following prebake conditions 90 seconds, form resist layer.In comprising the following embodiment of present embodiment, resist layer is set to and is thicker than the conventional thickness that is adopted, to carry out dissolubility test.
Novolac resin: the condensation polymer of m-cresol/p-cresol (6: 4) and formaldehyde.
Quinone diazido sensitising agent: 2,3,4,4 '-tetrahydroxybenzophenone and 1, the esterification products of 2-naphthoquinones diazido-5-sulfonic acid chloride.
In following solubility experiment, dissolubility to formed resist layer detects, employing to 1-(5), the results are shown in table 1 by the cleaning agent 1-(1) that forms with the propylene glycol list ethylether acetic acid esters (PGMEA) and the ethanol of different proportion as shown in table 1 in the experiment.
(solubility experiment)
The matrix that forms resist is thereon according to the method described above immersed in the 50ml cleaning agent, determine until all resist layer dissolvings and remove the used time (promptly dissolving the time) (unit: second) by naked eyes, divided by dissolution time, obtain dissolution velocity (/second) with the thickness () of resist layer.
Comparing embodiment 1 and 2
Repeat the identical process of embodiment 1, just adopt solvent PGMEA (comparing embodiment 1) separately or adopt etoh solvent (comparing embodiment 2) separately, obtain the result of table 1 as cleaning agent.
Table 1
Cleaning agent number Cleaning agent is formed (weight ratio) Dissolution velocity (/second)
1-(1) PGMEA *: ethanol=9: 1 7797
1-(2) PGMEA: ethanol=8: 2 10770
1-(3) PGMEA: ethanol=7: 3 18404
1-(4) PGMEA: ethanol=6: 4 19916
1-(5) PGMEA: ethanol=5: 5 13937
Comparing embodiment 1 PGMEA 100％ 2641
Comparing embodiment 2 Ethanol 100% Insoluble
*PGMEA: propylene glycol monomethyl ether
As shown in table 1, can increase dissolution velocity greatly by in PGMEA, adding ethanol.
Embodiment 2
Repeat the identical process of embodiment 1, just adopt by PGMEA and 1-propyl alcohol and be used as cleaning agent, obtain the result of table 2 with the solution that is shown in table 2 cleaning agent 2-(1) and forms to the ratio shown in the 2-(4).
Comparing embodiment 3
Repeat the identical process of embodiment 1, just adopt 1-propyl alcohol solvent separately, obtain the result of table 2 as cleaning agent.
Table 2
Cleaning agent number Cleaning agent is formed (weight ratio) Dissolution velocity (/second)
2-(1) PGMEA *: 1-propyl alcohol=9: 1 3318
2-(2) PGMEA: 1-propyl alcohol=8: 2 5224
2-(3) PGMEA: 1-propyl alcohol=7: 3 5672
2-(4) PGMEA: 1-propyl alcohol=6: 4 4843
Comparing embodiment 1 PGMEA 100％ 2641
Comparing embodiment 3 1-propyl alcohol 100% Insoluble
*PGMEA: propylene glycol monomethyl ether
As shown in table 2, mode that can be similar to Example 1 by adding 1-propyl alcohol in PGMEA increases dissolution velocity greatly.
Embodiment 3
Repeat the identical process of embodiment 1, just adopt by PGMEA and 2-propyl alcohol and be used as cleaning agent, obtain the result of table 3 with the solution that is shown in table 3 cleaning agent 3-(1) and forms to the ratio shown in the 3-(4).
Comparing embodiment 4
Repeat the identical process of embodiment 1, just adopt 2-propyl alcohol solvent separately, obtain the result of table 3 as cleaning agent.
Table 3
Cleaning agent number Cleaning agent is formed (weight ratio) Dissolution velocity (/second)
3-(1) PGMEA *: 2-propyl alcohol=9: 1 4543
3-(2) PGMEA: 2-propyl alcohol=8: 2 5128
3-(3) PGMEA: 2-propyl alcohol=7: 3 5659
3-(4) PGMEA: 2-propyl alcohol=6: 4 5350
Comparing embodiment 1 PGMEA 100％ 2641
Comparing embodiment 4 2-propyl alcohol 100% Insoluble
*PGMEA: propylene glycol monomethyl ether
As shown in table 3, can increase dissolution velocity greatly with embodiment 1 and 2 similar modes by in PG M EA, adding the 2-propyl alcohol.
Embodiment 4
Repeat the identical process of embodiment 1, just adopt by propylene glycol monomethyl ether (PGME) and ethanol and be used as cleaning agent, obtain the result of table 4 with the solution that is shown in table 4 cleaning agent 4-(1) and forms to the ratio shown in the 4-(4).
Comparing embodiment 5
Repeat the identical process of embodiment 1, just adopt the PGME solvent separately, obtain the result of table 4 as cleaning agent.
Table 4
Cleaning agent number Cleaning agent is formed (weight ratio) Dissolution velocity (/second)
4-(1) PGME **: ethanol=9: 1 6321
4-(2) PGME: ethanol=8: 2 9807
4-(3) PGME: ethanol=7: 3 14514
4-(4) PGME: ethanol=6: 4 10392
Comparing embodiment 5 PGME 100％ 4935
Comparing embodiment 2 Ethanol 100% Insoluble
*PGME: propylene glycol monomethyl ether
As shown in table 4, can increase dissolution velocity greatly by in PGME, adding ethanol.
Embodiment 5～10
Repeat the identical process of embodiment 1, just adopt by with n-butyl acetate, ethyl lactate, 2-heptanone, ethoxyl ethyl propionate, ethylene glycol monoethyl ether acetate or the methoxybutanol of ratio shown in the embodiment in the table 5 5～10 as organic solvent, the solution that ethanol is formed as alcohol obtains the result of table 5 as cleaning agent.
Comparing embodiment 6～11
Repeat the identical process of embodiment 1, just adopt n-butyl acetate, ethyl lactate, 2-heptanone, ethoxyl ethyl propionate, ethylene glycol monoethyl ether acetate or methoxybutanol as the independent solvent of organic solvent as cleaning agent, obtain the result of table 5.
Table 5
Cleaning agent is formed (weight ratio) Dissolution velocity (/second)
Embodiment 5 N-butyl acetate: ethanol=7: 3 5483
Embodiment 6 Ethyl lactate: ethanol=7: 3 859
Embodiment 7 2-heptanone: ethanol=7: 3 7550
Embodiment 8 Ethoxyl ethyl propionate: ethanol=7: 3 2371
Embodiment 9 Ethylene glycol monoethyl ether acetate: ethanol=7: 3 9142
Embodiment 10 Methoxybutanol: ethanol=7: 3 3921
Comparing embodiment 6 N-butyl acetate 100% 4421
Comparing embodiment 7 Ethyl lactate 100% 785
Comparing embodiment 8 2-heptanone 100% 5940
Comparing embodiment 9 Ethoxyl ethyl propionate 100% 2204
Comparing embodiment 10 Ethylene glycol monoethyl ether acetate 100% 4592
Comparing embodiment 11 Methoxybutanol 100% 1809
Comparing embodiment 2 Ethanol 100% Insoluble
Embodiment 11
Repeat the identical process of embodiment 1, just by the mixture of PGMEA, ethanol and 1-propyl alcohol (7: 2: 1, weight ratio) as cleaning agent, obtain the result of table 6.
Comparing embodiment 12
Repeat the identical process of embodiment 1, just with ethanol and 1-propyl alcohol (2: 1 weight ratios) as cleaning agent, obtain the result of table 6.
Table 6
Cleaning agent is formed (weight ratio) Dissolution velocity (/second)
Embodiment 11 PGMEA *: ethanol: 1-propyl alcohol=7: 2: 1 15185
Comparing embodiment 1 PGME100％ 2641
Comparing embodiment 12 Ethanol: 1-propyl alcohol=2: 1 Insoluble
*PGMEA: propylene glycol monomethyl ether
Any cleaning agent among the embodiment is all as safe as a house to human body.
The present invention sends out advantage
As mentioned above, compare with conventional cleaning agent, the present invention significantly improves for the solubility property of lithographic cleaning agent to resist, can adopt a small amount of cleaning agent to carry out rapid effective cleaning, and this cleaning agent is all very safe to human body.
Commercial Application
As mentioned above, the present invention is used for lithographic cleaning agent and can uses in the step of cleaning substrate and rinsing matrix at the coating resist, after removing resist and removing resist producing the semiconductor integrated circuit element.

Claims (1)

1, a kind ofly be used for lithographic cleaning agent, described cleaning agent is made up of a kind of homogeneous solution, and described homogeneous solution has the composition of one of the following,
Propylene glycol monomethyl ether and ethanol, weight ratio are 9: 1～1: 1,
Propylene glycol monomethyl ether and 1-propyl alcohol, weight ratio are 9: 1～3: 2,
Propylene glycol monomethyl ether and 2-propyl alcohol, weight ratio are 9: 1～3: 2,
Propylene glycol monomethyl ether, ethanol and 1-propyl alcohol, weight ratio is 7: 2: 1,
Propylene glycol monomethyl ether and ethanol, weight ratio are 9: 1～3: 2,
N-butyl acetate and ethanol, weight ratio are 7: 3,
Ethyl lactate and ethanol, weight ratio are 7: 3,
2-heptanone and ethanol, weight ratio are 7: 3,
Ethoxyl ethyl propionate and ethanol, weight ratio are 7: 3,
Ethylene glycol monoethyl ether acetate and ethanol, weight ratio are 7: 3, or
Methoxybutanol and ethanol, weight ratio are 7: 3.
CNB988008149A 1997-06-24 1998-06-17 Detergent for lithography Expired - Fee Related CN1185687C (en)

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JP167593/1997 1997-06-24
JP16759397A JP3978255B2 (en) 1997-06-24 1997-06-24 Lithographic cleaning agent

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CN1185687C true CN1185687C (en) 2005-01-19

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KR100578264B1 (en) 2006-05-11
TW591348B (en) 2004-06-11
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CN1229522A (en) 1999-09-22
EP0923112A1 (en) 1999-06-16

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